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Baker Hughes Downstream Chemicals

Shale Oil Impacts on Refining and Transportation

Baker HughesLarry Kremer

Shale Oil Processing Issues

• Wax deposits in tanks• Emulsion stabilization &

water hold up in crude oil • High filterable solids • Crude blending• Overhead corrosion

• Cold & hot train fouling• Fuel blending• Odor and hydrogen sulfide• Cold flow and lubricity

properties of fuels

Shale oil quality variability from one field

© 2012 Baker Hughes Incorporated. All Rights Reserved. 2

Characteristics of Shale Production

• Some times called ‘tight oil’• Horizontal drilling was key technology

advance• Hydraulic fracturing of shale formation• Infrastructure does not exist to meet needs

– Most shale oil moved by rail or trucks– Limited pipelines expanding to meet transportation needs

• Unit trains bring Bakken to east coast, west coast, and gulf coast• Truck transportation leads to quality fluctuations• As oil is consolidated into larger shipments, quality variations should

be reduced

© 2012 Baker Hughes Incorporated. All Rights Reserved. 3

Analytical - Eagle Ford Crude Variability

Value Yellow Red Black

API 55.0 44.6 52.3

TAN <0.05 0.07 <0.05

Sulfur <0.2% <0.2% <0.2%

Asphaltene 0% 0% 0.1%

Resin 0.5% 3.2% 1.6%

Filterable solids 176 PTB 295 PTB 225 PTB

© 2012 Baker Hughes Incorporated. All Rights Reserved. 4

Micrograph of Sludge

100 X

400 X

© 2012 Baker Hughes Incorporated. All Rights Reserved. 5

Paraffin Analysis Bottom of Sample

• Considerable high molecular weight wax in bottom• High MW = High melting point Some wax melts above 100ºC (212ºF)

© 2012 Baker Hughes Incorporated. All Rights Reserved. 6

Transportation Issues

• Incompatibility with asphaltenic crude oils

• Paraffin deposits

• H2S – HS&E issue

• Odor – Trains and trucks

• Mercaptans in Utica production

• Tendency to over treat with scavengers can lead to amines in crude unit

© 2012 Baker Hughes Incorporated. All Rights Reserved. 7

Shale Oil Hydrogen Sulfide

• Although low in S they can be high in H2S– HS&E concerns– Trucks and trains travel through towns– Fittings on sweet tanks may not handle H2S

• Misapplication can cause downstream issues– Excessive chemical use– Some scavengers can lead to downstream salting– Amine chlorides salts in overhead can be corrosive

© 2012 Baker Hughes Incorporated. All Rights Reserved. 8

Paraffin Deposits

• Transportation– Pipelines– Barges– Trains– Cold train exchangers

• Crude storage tank– Sludge increase– Wall deposits

• H/C Atomic Ratio =1.5 • 24% Fe + S• 63% C + H

Deposit Composition

mV

0.00

50.00

100.00

150.00

200.00

250.00

Minutes0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00 30.00

C11

C12

C13 C

14 C15

C16

C17

C18

C19

C20

C21

C22

C23

C24

C25

C26

C27

C28

C29

C30

C31

C32

C33 C34 C35 C36 C

37 C38 C

39C

40 C41

C42

C43 C

44C4

5 C46

C47 C

48C

49C

50C

51C

52C

53C

54C

55C

56C

57C

58C

59C

60C

61C

62C

63C

64C

65C6

6C

67C

68 C69 C70 C71 C72 C73

© 2012 Baker Hughes Incorporated. All Rights Reserved. 9

Cold Train Fouling Trial

• Customer must clean cold train exchangers every 10 days• Deposits have wax and asphaltene components• Developed new LIFESPAN™ fouling control additives• Treatment continued 6 months without cleaning shut down• Reduction in fouling so significant that customer will not

turn off chemical

© 2012 Baker Hughes Incorporated. All Rights Reserved. 10

LIFESPAN is a trademark of Baker Hughes Incorporated

Issues with Asphaltene Destabilization

• Shale oil can destabilize asphaltenic crude

• Problem shows up first as emulsion stabilization

– Oil in desalter brine– Increased BS&W

• Potential destabilization in tankage

• Asphaltene fouling of hot train• Customers have also seen cold train fouling• Destabilization can be quantified with the Field ASIT

services™ technologyField ASIT services is a trademark of Baker Hughes Incorporated.© 2012 Baker Hughes Incorporated. All Rights Reserved. 11

ASIT™ Asphaltene Stability Index Test• ASIT Test measures the onset of the flocculation of the asphaltenes

with high accuracy by inducing the asphaltene precipitation via titration with a paraffinic solvent

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ASIT is a trademark of Baker Hughes Incorporated

ASIT Blend of Bakken and Cold Lake

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Shale Oil Blending

• Paraffins destabilize asphaltenes• Negative impact on desalter operation

–Brine quality–Rag stability

• Can lead to fouling:–Cold train–Hot train–Furnace

© 2012 Baker Hughes Incorporated. All Rights Reserved. 14

Summary

• Shale oils are paraffinic– Low sulfur and TAN– Blending issues with asphaltenic crude oils

• Low sulfur but can have H2S– Apply correct product properly

• Paraffin content raises new fouling issues– Additives have demonstrated effective control

• Cold train fouling• Hot train fouling• Furnace fouling

© 2012 Baker Hughes Incorporated. All Rights Reserved. 15

© 2012 Baker Hughes Incorporated. All Rights Reserved. 16